Preparation and properties of pullulan–alginate–carboxymethylcellulose blend films

Pullulan, alginate, and carboxymethylcellulose (CMC) films were solvent cast from aqueous polymer solution. At 55% RH and 20 °C, their tensile strength and elongation at break were 67 MPa and 11%, 49 MPa and 5.2%, and 45 MPa and 5.8%, respectively. Pullulan films had lower water vapor permeability than alginate and CMC films (4.4 × 10⁻⁷, 9.7 × 10⁻⁷, and 1.3 × 10⁻⁶ g m/Pa h m², respectively), but dissolved in water quicker than alginate and CMC films. By incorporating alginate and CMC into pullulan, water barrier and mechanical properties were weakened significantly. Blending pullulan with alginate or CMC up to about 17–33% (w/w total polymer) reduced film solubilization time in water. The addition of glycerol further reduced tensile strength, increased elongation at break, weakened water barrier properties, but enhanced solubilization in water. FTIR results indicated that blending pullulan with alginate and CMC resulted in weaker hydrogen bonds acting on –OH groups compared to the pure pullulan.     

Calcium–Alginate–Inulin Microbeads as Carriers for Aqueous Carqueja Extract

Carqueja (Pterospartum tridentatum) is an endemic species and various bioactive compounds have been identified in its aqueous extract. The aim of this study was to protect the natural antioxidants from the aqueous extract of carqueja by encapsulation in Ca–alginate microbeads and Ca–alginate microbeads containing 10% and 20% (w/v) of inulin. The microbeads produced by electrostatic extrusion technique had an average diameter from 625 μm to 830 μm depending on the portion of inulin. The sphericity factor of the hydrogel microbeads had values between 0.014 and 0.026, while freeze dried microbeads had irregular shape, especially those with no excipient. The reduction in microbeads size after freeze drying process (expressed as shrinkage factor) ranged from 0.338 (alginate microbeads with 20% (w/v) of inulin) to 0.523 (plain alginate microbeads). The expressed radical scavenging activity against ABTS and DPPH radicals was found to be between 30% and 40% for encapsulated extract, while the fresh extract showed around 47% and 57% of radical scavenging activity for ABTS and DPPH radicals, respectively. The correlation between antioxidant activity and the total phenolic content were found to be positive (in both assay methods, DPPH and ABTS), which indicate that the addition of inulin didn't have influence on antioxidant activity. The presence of inulin reduced stiffness of the hydrogel, and protected bead structure from collapse upon freeze‐drying. Alginate–inulin beads are envisaged to be used for delivery of aqueous P. tridentatum extract in functional food products.     

Effects of glycerol,sorbitol, xylitol and fructose plasticisers on mechanical and moisture barrier properties of pullulan–alginate–carboxymethylcellulose blend films

The effects of glycerol, sorbitol, xylitol and fructose plasticisers on water sorption, mechanical properties, water vapour permeability (WVP) and microstructure of pullulan–alginate–carboxymethycellulose (PAC) blend films were investigated. At low plasticiser concentrations (below 7% w/w dry basis), antiplasticisation effect was observed, causing an increase in tensile strength (TS) but a decrease in the equilibrium moisture content. As glycerol concentration increased from 0% to 7%, TS increased from 68.1 to 69.6 MPa, whereas equilibrium moisture contents at 0.84 a_w decreased from 0.37 to 0.3 g H₂O g^?1 dry basis. At higher plasticiser concentrations (14–25% w/w), an opposite trend was observed on the PAC films, resulting in the reduction of TS and elevation of moisture content. Among the four plasticisers tested, the fructose‐plasticised films were the most brittle, showing the highest TS, but had the lowest elongation at break (EAB), WVP and equilibrium moisture content values than films plasticised with other polyols. On the other hand, glycerol resulted in the most flexible film structure, exhibiting opposite materials' properties as compared with the fructose‐plasticised films. For instance, at 25% (w/w) plasticiser concentration, EAB and WVP values of fructose‐plasticised films were 33.5% and 3.48 × 10^?6 g m Pa^?1 h^?1 m^?2, which were significantly lower than that of glycerol‐plasticised films (58.6% and 4.86 × 10^?6 g m Pa^?1 h^?1 m^?2, respectively). Scanning electron microscopy showed that the plasticised PCA films were less homogeneous and more porous than the unplasticised counterparts, indicating that plasticisers had an effect on the microstructural morphology of the film matrix.     

Mechanical and Microstructural Properties of “Wet” Alginate and Composite Films Containing Various Carbohydrates

Composite “wet” alginate films were manufactured from alginate–carbohydrate solutions containing 5% alginate and 0.25% pectin, carrageenan (kappa or iota), potato starch (modified or unmodified), gellan gum, or cellulose (extracted or commercial). The “wet” alginate films were used as a model to understand co‐extruded alginate sausage casings that are currently being used by several sausage manufacturers. The mechanical, optical, and microstructural properties of the calcium cross‐linked composite films were explored. In addition, the water holding capacity and textural profile analysis properties of the alginate–carbohydrate gels were studied. The results indicate that the mechanical properties of “wet” alginate films/casings can be modified by adding various carbohydrates to them. Alginate films with pectin, carrageenan, and modified potato starch had significantly (P < 0.05) greater elongation values than pure alginate films. The alginate–pectin films also had greater (P < 0.05) tensile strengths than the pure alginate films. Alginate films with extracted cellulose, commercial cellulose, and modified potato starch had lower (P < 0.05) puncture force, distance, and work values than the alginate control films. Transmission electron microscopy images showed a very uniform alginate network in the control films. Several large cellulose fibers were visible in the films with extracted cellulose, while the cellulose fibers in the films with commercial cellulose were difficult to distinguish. Despite these apparent differences in cellulose fiber length, the 2 cellulose films had similar puncture and tensile properties.     

Release Kinetics of Nisin from Chitosan–Alginate Complex Films

Understanding the release kinetics of antimicrobials from polymer films is important in the design of effective antimicrobial packaging films. The release kinetics of nisin (30 mg/film) from chitosan–alginate polyelectric complex films prepared using various fractions of alginate (33%, 50%, and 66%) was investigated into an aqueous release medium. Films containing higher alginate fractions showed significantly lower (P < 0.05) degree of swelling in water. Total amount of nisin released from films into an aqueous system decreased significantly (P < 0.05) with an increase in alginate concentration. The mechanism of diffusion of nisin from all films was found to be Fickian, and diffusion coefficients varied from 0.872 × 10^?9 to 8.034 ×10^?9 cm²/s. Strong complexation was confirmed between chitosan and alginate polymers within the films using isothermal titration calorimetry and viscosity studies, which affects swelling of films and subsequent nisin release. Complexation was also confirmed between nisin and alginate, which limited the amount of free nisin available for diffusion from films. These low‐swelling biopolymer complexes have potential to be used as antimicrobial packaging films with sustained nisin release characteristics.     

Changes of microwave structure/dielectric properties during microwave freeze‐drying process banana chips

This experimental study investigated the trend of structure and dielectric properties during microwave freeze‐drying process banana chips. The mass of banana samples was 160 g, the microwave power set as 2 W g^?1 and the highest drying temperature set as 55 °C. The whole drying process can be finished within 6 h. A network analyser and light microscope were used to determine the dielectric properties and structure. The dielectric properties, ε′ (from 20.80 to 1.20) and ε′′ (from 7.74 to 0.15), and the size of cell get smaller as the drying process continues, especially during the 3–4 h drying, which is the end of primary drying stage and the beginning of secondary drying stage. The trend of dielectric properties and microstructure of samples during drying can be an exact indication of drying stage of MFD.     

Starch–methylcellulose–whey protein film properties

Four % (wt/wt) aqueous solutions were prepared at corn starch:methylcellulose:whey protein isolate (CS:MC:WPI) ratios of 2:2:2, 1:2:3, 2:1:3, 2:2:0, 1:2:0 and 2:1:0. Glycerol (gly) was used as a plasticiser at CS–MC–WPI:gly ratios of 2:1, 2.5:1 and 3:1. CS–MC–WPI blend films were stronger than CS–WPI films and had lower oxygen permeability (OP) than MC–WPI films. The highest tensile strength (TS) of blend films was 8.01 ± 3.41 MPa, at CS:MC:WPI ratio of 2:2:0 and CS–MC–WPI:gly ratio of 3:1. Lowest OP value was 45.05 ± 7.24 cm³ μm m^?2 per day kPa^?1, at CS:MC:WPI ratio of 2:2:2 and CS–MC–WPI:gly ratio of 3:1. OP values were predictable based on relative amounts of components. However, TS and elastic modulus properties of the CS–MC–WPI blend films did not reflect the relative amounts of the components. All of CS–MC–WPI films were translucent indicating some degree of immiscibility among the CS, MC and WPI. These results indicate the influence of complex molecular interactions among the components.     

Moisture migration by magnetic resonance imaging during eggplant drying: a preliminary study

The paper investigated the effect of hot‐air drying (50, 60 °C) on the physical properties of cylindrical eggplant samples. Drying kinetics, water profiles along longitudinal and transversal sample sections through nuclear magnetic resonance imaging (MRI) and volumetric shrinkage were determined. During the drying process at 50 °C, the volume of removed water was found lower than the reduction in sample volume, while at 60 °C it was higher. MRI showed that the water migration mainly occurs transversally than longitudinally. The curves of mass water loss obtained by both the standard weighting method and MRI showed conformity. Experimental data of moisture ratio and of shrinkage volume were fitted using empirical models available in the literature. This preliminary study showed that the nondestructive MRI technique offers the possibility to study water distribution in food during drying processes. The quantitative moisture distribution maps allow future development and verification of models for prediction of mass transport phenomena in foods during drying.     

Understanding forced convective drying of apple tissue: Combining neutron radiography and numerical modelling

A multiphysics model for biological materials, coupling nonlinear viscoelastic deformation to water transport, was used to study forced convective drying of apple tissue samples (cv. Maigold). The accuracy of the model was verified with quantitative neutron radiography experiments, by comparing the total water loss, the transient water distribution profiles and the mechanical deformation. Both model simulations and experiments showed that the largest moisture gradients occurred at the air–tissue interface. The corresponding shrinkage behaviour was similar. Furthermore, the difference between simulation results from modelling the water exchange with the environment using a constant mass transfer coefficient or a spatially varying transfer coefficient from a flat-plate correlation was not significant, indicating that the drying kinetics were dominated by the water transport in the tissue rather than by the convective flow at air–tissue interface. The simulated results showed a satisfactory agreement with experimental observations. The validated model is clearly appropriate to be employed for optimization of convective drying processes of food.Industrial RelevanceThe paper adds a significant progress to the study the dynamics of drying (water transport and shrinkage) during dehydration of fruit tissue.     

Modeling Simultaneous Shrinkage and Heat and Mass Transfer of a Thin, Nonporous Film During Drying

Thin films of food products have long been dried commercially but the thin film drying process is not well understood. Modeling of a drying system is essential for understanding and improving it. A theoretical model for predicting the drying rate of thin films of nonporous foods was proposed, developed and evaluated. The model simultaneously considered shrinkage and heat and mass transfer within thin films dried on a surface with given boundary conditions. A finite element formulation of the model was used to develop numerical solutions of two governing equations. Starch was selected as a representative material for drying tests. Experimentally determined drying curves of modified corn, potato and rice starch films were compared to model predictions. The technique was useful in explaining the complex relationships of temperature, moisture and thickness profiles of drying films.     

Preparation of Acid‐Resistant Microcapsules with Shell‐Matrix Structure to Enhance Stability of Streptococcus Thermophilus IFFI 6038

Microencapsulation is an effective technology used to protect probiotics against harsh conditions. Extrusion is a commonly used microencapsulation method utilized to prepare probiotics microcapsules that is regarded as economical and simple to operate. This research aims to prepare acid‐resistant probiotic microcapsules with high viability after freeze‐drying and optimized storage stability. Streptococcus thermophilus IFFI 6038 (IFFI 6038) cells were mixed with trehalose and alginate to fabricate microcapsules using extrusion. These capsules were subsequently coated with chitosan to obtain chitosan‐trehalose‐alginate microcapsules with shell‐matrix structure. Chitosan‐alginate microcapsules (without trehalose) were also prepared using the same method. The characteristics of the microcapsules were observed by measuring the freeze‐dried viability, acid resistance, and long‐term storage stability of the cells. The viable count of IFFI 6038 in the chitosan‐trehalose‐alginate microcapsules was 8.34 ± 0.30 log CFU g^?1 after freeze‐drying (lyophilization), which was nearly 1 log units g^?1 greater than the chitosan‐alginate microcapsules. The viability of IFFI 6038 in the chitosan‐trehalose‐alginate microcapsules was 6.45 ± 0.09 log CFU g^?1 after 120 min of treatment in simulated gastric juices, while the chitosan‐alginate microcapsules only measured 4.82 ± 0.22 log CFU g^?1. The results of the long‐term storage stability assay indicated that the viability of IFFI 6038 in chitosan‐trehalose‐alginate microcapsules was higher than in chitosan‐alginate microcapsules after storage at 25 °C. Trehalose played an important role in the stability of IFFI 6038 during storage. The novel shell‐matrix chitosan‐trehalose‐alginate microcapsules showed optimal stability and acid resistance, demonstrating their potential as a delivery vehicle to transport probiotics.     

Optimisation of convective drying of carrots using selected processing and quality indicators

The effect of drying temperature (40–65 °C) and air rate (2–6 m s^?1) on the formation of Maillard reaction indicators and vitamins content of carrots dehydrated by convection has been investigated. The range of assayed processing conditions, based on a previous central composite face design (CCD), led to moderate changes in the studied parameters, even under the most severe conditions. In addition, the drying kinetic of the process was studied taking into account the experimental quantitation of shrinkage, which allowed the determination of a first drying period with a constant rate of water evaporation per unit of exchange surface. The slope of the first drying period, the moisture loss during the first hour of drying and the level of quality parameters (Maillard reaction indicators and vitamins) were correlated with processing conditions with high accuracy. For the prototype here used, the optima temperature and air rate to maximise the desirability function (0.77) were 46 °C and 4.9 m s^?1.     

Effect of combined microwave‐hot air drying and superheated steam drying on physical and chemical properties of rice

Jasmine rice (Oryza sativa L.) was subjected to two drying operations: combined microwave‐hot air drying (MHA) at initial power intensity of 3, 4 and 6 W g^?1 and superheated steam drying (SHS) at 300 °C and 400 °C. During drying, kinetic rate constants of SHS were significantly higher than those of MHA. Both drying operations could decrease enthalpy of starch gelatinisation from 9.28 J g^?1 to 1.64–6.17 J g^?1, increase gelatinisation extent to 33.51–82.33%, decrease crystallinity from 28.87% to 18.15–21.33%, improve scavenging ability of 1,1‐diphenyl‐2‐picrylhydrazyl, increase ferric reducing antioxidant power and increase hardness of cooked rice from 5.66 N to 5.83–6.55 N, depending on microwave power and drying medium temperature. However, taste profiles and liking scores were comparable to the regular brown rice. Therefore, MHA and SHS operations could be potentially used for reducing drying process and promoting antioxidant activity.     

Preparation and characterisation of selected physicochemical and functional properties of β‐chitosans from squid pen

Squid pen β‐chitosans prepared under various deacetylation conditions (30%, 35%, 40% and/or 45% NaOH for 15, 30 and/or 60 min) were characterised. β‐Chitosans (deacetylated with 35–45% NaOH for 15–60 min) had 87.1–96.2% degree of deacetylation (DD), 93.5–96.7% solubility and 120.5–654.9 mPa s viscosity. Treatment with 30% NaOH for 15–60 min yielded inadequately deacetylated β‐chitosans (DD = 51.9–80.2%). Two chitosans prepared under 35% NaOH for 15 min and 45% NaOH for 30 min (designated as 35%–15 and 45%–30, respectively) were further compared. Drying (sun‐drying vs. oven‐drying) methods did not affect DD. 35%–15 chitosan exhibited lower nitrogen, DD and bulk density, but higher viscosity compared with 45%–30 chitosan. Higher water‐ and fat‐binding capacity but lower DPPH radical scavenging activity were observed for 35%–15 chitosan compared with 45%–30 chitosan. Compared with 45%–30 chitosan, 35%–15 chitosan exhibited higher antibacterial activity against Salmonella Enteritidis and Listeria monocytogenes, but lower antibacterial activity against Escherichia coli.     

Drying characteristics and thermal degradation kinetics of hardness,anthocyanin content and colour in purple‐ and red‐fleshed potato (Solanum tuberosum L.) during hot air drying

Purple‐fleshed potatoes (PFP) and red‐fleshed potatoes (RFP) were dried using hot air. The hardness, anthocyanin content and colour in PFP and RFP during drying were evaluated at 60, 70 and 80 °C. The hardness was characterised by a softening stage in the early drying period, followed by a hardening stage. The times to reach at the transition were 420, 300 and 240 min at 60, 70 and 80 °C, respectively, for PFP, and 480, 360 and 240 min for RFP. However, the moisture content of both PFP and RFP at the transition time was identical at 0.3 (d.b.). The two stages of hardness changes were well described by combining two modified first‐order kinetics models. The activation energy (E_a) for the degradation of anthocyanin in PFP and RFP was 25.12 and 28.43 kJ mol^?1, respectively. The E_a values demonstrated that the thermal sensitivity of PFP was higher than that of RFP.     

Efficacy of Antimicrobial Pullulan‐Based Coating to Improve Internal Quality and Shelf‐Life of Chicken Eggs During Storage

There has been a growing interest in the use of natural materials as a delivery mechanism for antimicrobials and coatings in foods. The aim of the present study was to evaluate the effectiveness of pullulan coatings to improve internal quality and shelf‐life of fresh eggs during 10 wk of storage at 25 and 4 °C. Three treatments of eggs were evaluated as follows; non‐coated (control; C), coated with pullulan (P), and coated with pullulan containing nisin (N). The effects of the pullulan coatings on microbiological qualities, physical properties, and freshness parameters were investigated and compared with non‐coated eggs. For non‐coated eggs, as storage time increased, yolk index, albumen index, and Haugh unit value decreased and weight loss increased. However, pullulan coatings (P or N) minimized weight loss (<1.5%) and preserved the albumen and yolk quality of eggs (with a final B grade) 3 wk longer than non‐coated eggs at 25 °C. At 4 °C, both P‐ and N‐coated eggs went from AA to A grade after 9 wk and maintained the grade for 10 wk (4 wk longer than that of non‐coated eggs). This study is the first to demonstrate that pullulan coatings can preserve the internal quality, prolong the shelf‐life, and minimize weight loss of fresh eggs.     

Improvement on Physical Properties of Pullulan Films by Novel Cross‐Linking Strategy

Pullulan based films possess several advantages, including high transparency, low toxicity, good biodegradability, good mechanical properties, and low oxygen permeability, are preferable for food packaging. The application of pullulan films on food packaging, however, has inherent disadvantage of high water solubility. In this study, glutaraldehyde and glycerol were used as the cross‐linking reagent and the plasticizer respectively to improve water resistance and physical properties of the pullulan films. Effects of cross‐linking degree on physical properties, including water absorptions, swelling behaviors, water vapor permeability and tensile strengths of films were evaluated. FTIR results demonstrated that the pullulan films were successfully cross‐linked by glutaraldehyde. The tensile strength of pullulan films could be enhanced significantly (P < 0.05) when glutaraldehyde was between 1% and 5% (w/w); nevertheless, the amount of glutaraldehyde above 20% (w/w) led to films brittleness. With the addition of glycerol as a plasticizer enhanced the extensibility of films as well as the hydrophilicity, resulting in higher water vapor permeability.     

Physicochemical properties and application of pullulan edible films and coatings in fruit preservation

The effects of water, sorbitol and a sucrose fatty acid ester (SE) on the water sorption behaviour and thermal and mechanical properties of pullulan‐based edible films as well as the physiological responses of fruit coated with pullulan have been studied. Incorporation of sorbitol or SE in pullulan films resulted in lower equilibrium moisture contents at low to intermediate water activities (a_w), but much higher moisture contents at a_w > 0.75; estimates of monolayer values (within 4.1–5.9 gH₂O kg^?1 solids) were given by application of the Brunauer–Emmett–Teller (BET) and Guggenheim–Anderson–DeBoer (GAB) models. A single glass–rubber transition (T_g), attributed to the polysaccharide component, was detected by calorimetry and dynamic mechanical thermal analysis (DMTA) at a sorbitol level of 15–30% DM. With both tests the strong plasticising action of water and polyol was evident in the thermal curves, and the T_g vs moisture content data were successfully fitted to the Gordon–Taylor empirical model. Multifrequency DMTA measurements provided estimates for the apparent activation energy of the glass transition in the range of ? 300–488 kJ mol^?1. With large‐deformation mechanical testing, large decreases in Young's moduli (tensile and three‐point bend tests) were observed as a result of water‐ and/or polyol‐mediated glass‐to‐rubber transition of the polymeric films. In the moisture content range of 2–8%, increases in flexural modulus (E) and maximum stress (σ_max) with small increases in moisture content were found for films made of pullulan or pullulan mixed with 15% DM sorbitol; a strong softening effect was observed when the water content exceeded this range. Addition of sorbitol increased the water vapour transmission rate of the films, whereas addition of SE had the opposite effect. Application of a pullulan/sorbitol/SE coating on strawberries resulted in large changes in internal fruit atmosphere composition which were beneficial for extending the shelf‐life of this fruit; the coated fruit showed much higher levels of CO₂, a large reduction in internal O₂, better firmness and colour retention and a reduced rate of weight loss. In contrast, similar studies on whole kiwifruits showed increased levels of internal ethylene, which caused acceleration of fruit ripening during storage. © 2001 Society of Chemical Industry     

Properties of konjac glucomannan–whey protein isolate blend films

Edible composite packaging has been developed by blending biocomponents for specific applications, aiming to take advantage of complementary functional properties or to overcome their respective flaws. The aim of this work was to study the effect of incorporation of whey protein isolate (WPI) on the properties of konjac glucomannan (KGM) based films. Five aqueous solutions of KGM and/or WPI were prepared by casting and solvent evaporation of 1:0, 0.8:3.4, 0.6:3.6, 0.4:3.8 and 0:4.2 g KGM:g WPI/100 g solution. Glycerol (Gly) was used as a plasticizer at 1.5 and 1.8 g/100 g solution. The result showed that incorporated WPI proportionally increased transparency of KGM-based films. An increase in proportion of WPI resulted in decreased tensile strength and elastic modulus as well as improved flexibility. The incorporation of WPI into the KGM matrix led to an increase in water insolubility which enhanced product integrity and water resistance. Nevertheless, WPI did not improve water vapor barrier of KGM–WPI films. WPI and blend film with the highest concentration of WPI could be heat sealed at 175 °C. Overall, the range of Gly in this study did not apparently affect properties of the films.     

Effect of Glycerol on Water Vapor Sorption and Mechanical Properties of Starch/Clay Composite Films

Plasticized starch/clay composite films were prepared by casting aqueous solutions containing oxidized corn starch, different concentrations of glycerol as a plasticizer and 5% clay (sodium montmorillonite, Na⁺‐MMT) on the basis of dry starch. The water‐binding properties of the composite films were evaluated by water vapor sorption isotherms at room temperature and various relative humidities (RHs). Mechanical properties and abrasion resistance were also analyzed for the films with varying glycerol contents at 68% RH and room temperature. Changes in water sorption isotherms suggested that glycerol interacted with both water and starch in a complicated way. A saturation phenomenon of glycerol, depending on RH, was observed based on the isotherms. Above this saturation content, phase separation of the system occurred with the appearance of free glycerol. According to mechanical performance and abrasion resistance, as well as water vapor sorption of the starch blend films, the three‐stage transition was presented to be related to the state of glycerol in the blend system, i.e. adsorption of glycerol onto H‐bonding sites of starch, supersaturation of glycerol as plasticizer and further supersaturation of glycerol. Only above the supersaturation content can glycerol play a plasticizer role in starch‐based composites.